CN105080576A - Method for activating MoVNbTeOx pure-phase M1 catalyst by utilizing plasma gas-solid phase method - Google Patents
Method for activating MoVNbTeOx pure-phase M1 catalyst by utilizing plasma gas-solid phase method Download PDFInfo
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Abstract
The invention provides a method for activating a MoVNbTeOx pure-phase M1 catalyst by utilizing a plasma gas-solid phase method. The method comprises the following steps: preparing an MoVNbTeOx M1 and M2 mixed-phase catalysts by using a hydrothermal synthetic method, then subjecting the mixed-phase catalyst to hydrogen oxide purification process so as to obtain an MoVNbTeOx-system M1 pure-phase compound, and carrying out plasma treatment of oxygen and enhancing the content of pentavalent vanadium on the surface of the catalyst so as to obtain the MoVNbTeOx pure-phase M1 catalyst with more excellent catalytic effects. According to the invention, the concentration of the pentavalent vanadium is increased under the condition of no change of the total content of a vanadium element; meanwhile, stability of the structure of the catalyst can be kept. The catalyst obtained by plasma treatment can significantly improve activity thereof in the process of oxidative dehydrogenation of ethane. The plasma gas-solid phase method provided by the invention is employed to modify the catalyst, so quality loss of traditional hydrogen peroxide aqueous-phase treatment is reduced.
Description
Technical field
The present invention is specifically related to one and utilizes plasma gas solid method to activate the method for MoVNbTeOx (molybdenum vanadium niobium tellurium multi-element metal oxide) pure phase M1 catalyst.
Background technology
Ethene is one of maximum in the world chemical products, is also most important basic material in petroleum industry.Ethylene product accounts for more than 75% of petroleum chemicals, and its output is one of important symbol of a measurement national oil development of chemical industry level.
At present, naphtha and ethane steam cracking technique are the ethylene production technique be most widely used in the world.The hydrocarbons such as naphtha are considered to consume energy in petroleum chemical industry the highest process as the steam cracking process of raw material, and the burning of byproduct result also in the discharge of great amount of carbon dioxide.
Making ethylene from ethane oxidative dehydrogenation has more advantage compared to realizing industrialized steam cracking, but is limited to the Exploitation degree of current catalyst productivity and relevant reactor, and this process not yet realizes large-scale industrial production.
In molybdenum vanadium niobium tellurium multi-element metal oxide system, M1 pure phase catalyst is the catalyst system at present with larger application prospect, under lower reaction temperature, have higher ethane conversion and ethylene selectivity.
The synthetic method of M1 pure phase catalyst comprises Hydrothermal Synthesis or the precipitation method, is aided with suitable purge process.This preparation process is complicated, and synthetic product is comparatively responsive to the Parameter Conditions of preparation process.
Usually, the vanadium of M1 pure phase catalyst surface exists with tetravalence and pentavalent two kinds of forms.Pentavalent vanadium is alkane activation site.Therefore the key factor of M1 pure phase catalyst system catalytic effect is the concentration of its surperficial pentavalent vanadium.
Traditional oxidation reduction catalyst needs to be oxidized catalyst more than 600 DEG C, and the structure of molybdenum vanadium niobium tellurium composite metal oxide system can be totally disrupted with this understanding.
Can be improved the concentration of catalyst surface pentavalent vanadium by the hydrogen peroxide process pure phase M1 catalyst of high concentration, but the method is Aqueous phase, uses the hydrogen peroxide of 15 ~ 20%, a large amount of mass losses can be caused.
Therefore, under comparatively gentle condition, how to regulate and control the pentavalent vanadium concentration of catalyst surface, thus the catalytic effect improving catalyst is a major issue in catalyst development.
Summary of the invention
The object of this invention is to provide a kind of plasma gas solid method that utilizes activates for the method for the MoVNbTeOx pure phase M1 catalyst of oxidative dehydrogenation of ethane, by carrying out atmospheric low-temperature plasma process to pure phase M1 catalyst, the ratio of regulation and control catalyst surface pentavalent vanadium and tetravalence vanadium, thus reach the object of optimization of catalysts catalytic activity.
Technical scheme of the invention process is as follows:
Utilize plasma gas solid method to activate a method for MoVNbTeOx pure phase M1 catalyst, it is characterized in that, the method comprises the steps:
1) obtain MoVNbTeOx system M1 and M2 mixed phase catalyst by hydrothermal synthesis method, obtain M1 pure phase catalyst through hydrogen peroxide purification process;
2) M1 pure phase catalyst is utilized pure oxygen, or with the gaseous mixture of oxygen and inert gas for carrier gas, under normal pressure or vacuum are 0.5 ~ 100mbar condition, carry out Low Temperature Plasma Treating; The input power of plasma treatment is 30 ~ 100W, and plasma treatment time is 5min ~ 100min.
Low temperature plasma of the present invention is preferably atmospheric dielectric stop and puts a plasma.
In technique scheme, when carrier gas adopts the mist of oxygen and inert gas, the ratio of oxygen is 20% ~ 80%.
In technical scheme of the present invention, step 1) described in the hydro-thermal method method that obtains MoVNbTeOx mixed phase catalyst comprise the steps:
1) under 60 ~ 80 DEG C of water bath condition, ammonium molybdate, vanadic sulfate and telluric acid are obtained solution A according to the ratio mixed dissolution that the atom of molybdenum and vanadium, tellurium is 1:0.15-0.30:0.15-0.35 in deionized water, ammonium niobium oxalate is dissolved in deionized water and obtains solution B, wherein in niobium and solution A, the atomic ratio of molybdenum is 0.05:1 ~ 0.20:1, the volume ratio of solution A and solution B is 2:1, mix after solution A and solution B are cooled to 30 ~ 50 DEG C and stir, forming precursor solution;
2) precursor solution is placed in water heating kettle, after replacing air wherein with nitrogen, the Hydrothermal Synthesis carrying out 24 ~ 48h at 150 ~ 200 DEG C obtains suspension;
3) suspension obtained by Hydrothermal Synthesis carries out washing and filtering, and grinding after gained sediment spends the night and dries, obtains the solid phase presoma of catalyst;
4) by solid phase presoma 550 ~ 650 DEG C of temperature lower calcinations in nitrogen atmosphere, calcination time is 1 ~ 3h, obtains the mixed phase compound of M1 and M2 in MoVNbTeOx system.
In the method for the invention, step 1) in obtain pure phase M1 catalyst by MoVNbTeOx system M1 and M2 mixed phase catalyst method be: M1 and M2 mixed phase catalyst is placed in the hydrogen peroxide that volume fraction is 5%, 1 ~ 3h is stirred at 50 ~ 70 DEG C of temperature, then carry out centrifugal, after removing supernatant, dry 12 ~ 24h, namely obtains M1 pure phase catalyst fines in MoVNbTeOx system.
The present invention compared with prior art, have the following advantages and the technique effect of high-lighting: the 1. method utilizing plasma treatment molybdenum vanadium niobium tellurium composite oxides pure phase M1 catalyst of the present invention, effectively can reduce required hydrogen peroxide concentration in processing procedure, thus decrease the mass loss in preparation process.2. the method utilizing plasma treatment molybdenum vanadium niobium tellurium composite oxides pure phase M1 catalyst of the present invention, effectively can promote catalyst surface pentavalent vanadium concentration.And pentavalent vanadium is as avtive spot unique in catalysis oxidative dehydrogenation of ethane process, its content promotes the catalytic activity that effectively can improve catalyst.3. the method utilizing plasma treatment molybdenum vanadium niobium tellurium composite oxides pure phase M1 catalyst of the present invention, by the means of gas solid method, without the need to unit such as filtration, dryings, technique is simple, and the processing time is short, and production efficiency is higher.
Accompanying drawing explanation
Fig. 1 be in embodiment 1 pentavalent vanadium and tetravalence vanadium ratio with the variation diagram in processing time.
Fig. 2 is without the catalyst of plasma treatment and the catalytic effect comparison diagram after vacuum oxygen argon plasma process 10min in embodiment 2.
Fig. 3 is without the catalyst of plasma treatment and the catalytic effect comparison diagram after pure oxygen atmospheric pressure plasma jet treatment 40min in embodiment 3.
Fig. 4 is without the catalyst of plasma treatment and the catalytic effect comparison diagram after oxygen argon atmospheric pressure plasma jet treatment 80min in embodiment 4.
Detailed description of the invention
One provided by the invention utilizes plasma gas solid method to activate the method for MoVNbTeOx (molybdenum vanadium niobium tellurium multi-element metal oxide) pure phase M1 catalyst, and it specifically comprises the steps:
1) obtain MoVNbTeOx system M1 and M2 mixed phase catalyst by hydrothermal synthesis method, obtain M1 pure phase catalyst through hydrogen peroxide purification process;
2) M1 pure phase catalyst is placed in the region of discharge of plasma processing apparatus, treating apparatus passes into carrier gas 1 ~ 2min, by after-applied for air emptying voltage; Adopt with pure oxygen, or oxygen and inert gas (ratio of oxygen is 20% ~ 80%), be carrier gas, process under normal pressure or vacuum are 0.5 ~ 100mbar condition, the input power of plasma treatment is 30 ~ 100W, and plasma treatment time is 5min ~ 100min.Low temperature plasma of the present invention preferably adopts Atmospheric DBD Plasma (dielectric impedance puts a plasma).
What the present invention adopted utilizes the concrete steps of the method for plasma gas solid method activation pure phase M1 catalyst to comprise:
Present invention also offers the M1 pure phase compounds process for production thereof in a kind of MoVNbTeOx (molybdenum vanadium niobium tellurium multi-element metal oxide) system, it specifically comprises:
1) under 60 ~ 80 DEG C of water bath condition, be the ammonium molybdate of 1:0.15-0.30:0.15-0.35 by the atomic ratio of molybdenum, vanadium and tellurium, vanadic sulfate, telluric acid mixed dissolution obtain solution A in deionized water, ammonium niobium oxalate is dissolved in deionized water and obtains solution B, wherein in niobium and solution A, the atomic ratio of molybdenum is 0.05:1 ~ 0.20:1, the volume ratio of solution A and solution B is 2:1, mixes and the formation precursor solution that stirs after solution A and solution B are cooled to 40 DEG C;
2) precursor solution is placed in water heating kettle, after replacing air wherein with nitrogen, the Hydrothermal Synthesis carrying out 24 ~ 48h at 150 ~ 200 DEG C obtains suspension;
3) suspension obtained by Hydrothermal Synthesis carries out washing and filtering, and grinding after gained sediment spends the night and dries, obtains the solid phase presoma of catalyst;
4) by solid phase presoma 550 ~ 650 DEG C of temperature lower calcinations in nitrogen atmosphere, calcination time is 1 ~ 3h, obtain the mixed phase compound of M1 and M2 in molybdenum vanadium niobium tellurium multi-element metal oxide system, this mixed phase compound is placed in the hydrogen peroxide that volume fraction is 5%, 1 ~ 3h is stirred at 50 ~ 70 DEG C of temperature, after removing supernatant, dry 12 ~ 24h, namely obtains M1 pure phase catalyst in molybdenum vanadium niobium tellurium multi-element metal oxide system.
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
Under 80 DEG C of water bath condition, be the ammonium molybdate of 1:0.26:0.25 by the atomic ratio of molybdenum and vanadium, tellurium, vanadic sulfate, telluric acid mixed dissolution obtain solution A in deionized water, ammonium niobium oxalate is dissolved in deionized water and obtains solution B, wherein in niobium and solution A, the atomic ratio of molybdenum is 0.13:1, solution A and solution B volume ratio are 2:1, mix and the formation precursor solution that stirs after solution A and solution B are cooled to 40 DEG C.
Precursor solution is placed in water heating kettle, after replacing air wherein with nitrogen, the Hydrothermal Synthesis carrying out 72h at 150 DEG C obtains suspension, and the suspension obtained by Hydrothermal Synthesis carries out washing and filtering, gained precipitates overnight grinds after drying, and obtains the solid phase presoma of catalyst.Solid phase presoma carries out 4h in nitrogen atmosphere calcining at 550 DEG C obtains the mixed phase compound of M1 and M2 in molybdenum vanadium niobium tellurium multi-element metal oxide system, be placed on after stirring 2h in the hydrogen peroxide of 5% volume fraction at 60 DEG C and carry out filtration and dried overnight, namely obtain M1 pure phase catalyst in molybdenum vanadium niobium tellurium multi-element metal oxide system.
Get the above-mentioned catalyst of 1.2g, get 0.2g catalyst at every turn and be placed in plasma processing apparatus, at normal temperatures, pass into the gaseous mixture of 50% oxygen and 50% argon gas, open plasma generating means after displaced air 1min, input power is 63W.Respectively catalyst is carried out to the plasma treatment of 10min, 20min, 40min, 60min and 80min.The catalyst processed respectively is carried out XPS test, obtains the ratio of pentavalent vanadium and tetravalence vanadium.This ratio over time as shown in Figure 1.
Embodiment 2
Identical with the method that embodiment 1 obtains pure phase M1 catalyst.Get 0.6gM1 pure phase catalyst, be placed in plasma processing apparatus, at normal temperatures, pass into the gaseous mixture of 50% oxygen and 50% argon gas, after displaced air 1min, open vavuum pump, when vacuum is down to 80mbar, open plasma generating means, input power is 70W.Catalyst is carried out to the plasma treatment of 10min, obtain the catalyst being used for oxidative dehydrogenation of ethane process.
Get above-mentioned catalyst after oxygen plasma treatment and undressed pure phase M1 catalyst 0.5g, with 5.0g carborundum dilution mixture be placed on fixed bed micro-anti-in, carry out catalyst performance test respectively.Be 400 DEG C in reaction temperature, reaction pressure is 1atm, and in unstripped gas, ethane, oxygen and helium mol ratio are 3:2:5, carry out oxidative dehydrogenation of ethane reaction under the condition of raw gas flow 30 ~ 90ml/min.Evaluating catalyst result as shown in Figure 2.
Embodiment 3
Identical with the method that embodiment 1 obtains pure phase M1 catalyst.Get 0.6gM1 pure phase catalyst, be placed in plasma processing apparatus, at normal temperatures, pass into oxygen, open plasma generating means after displaced air 1min, input power is 70W, catalyst is carried out to the plasma treatment of 40min, obtain the catalyst being used for oxidative dehydrogenation of ethane process.
Get above-mentioned catalyst after oxygen plasma treatment and undressed pure phase M1 catalyst 0.5g, with 5.0g carborundum dilution mixture be placed on fixed bed micro-anti-in, carry out catalyst performance test respectively.Be 400 DEG C in reaction temperature, reaction pressure is 1atm, and in unstripped gas, ethane, oxygen and helium mol ratio are 3:2:5, carry out oxidative dehydrogenation of ethane reaction under the condition of raw gas flow 30 ~ 90ml/min.Evaluating catalyst result as shown in Figure 3.
Embodiment 4
Identical with the method that embodiment 1 obtains pure phase M1 catalyst.Get 0.6gM1 pure phase catalyst, be placed in plasma processing apparatus, pass into the gaseous mixture of 50% oxygen and 50% argon gas.Open plasma generating means after displaced air 1min, input power is 84W.Catalyst is carried out to the plasma treatment of 80min, obtain the catalyst being used for oxidative dehydrogenation of ethane process.
Get above-mentioned catalyst after oxygen plasma treatment and undressed pure phase M1 catalyst 0.5g, with 5.0g carborundum dilution mixture be placed on fixed bed micro-anti-in, carry out catalyst performance test respectively.Be 400 DEG C in reaction temperature, reaction pressure is 1atm, and in unstripped gas, ethane, oxygen and helium mol ratio are 3:2:5, carry out oxidative dehydrogenation of ethane reaction under the condition of raw gas flow 30 ~ 90ml/min.Evaluating catalyst result as shown in Figure 4.
Claims (5)
1. utilize plasma gas solid method to activate a method for MoVNbTeOx pure phase M1 catalyst, it is characterized in that, the method comprises the steps:
1) obtain MoVNbTeOx system M1 and M2 mixed phase catalyst by hydrothermal synthesis method, obtain M1 pure phase catalyst through hydrogen peroxide purification process;
2) M1 pure phase catalyst is utilized pure oxygen, or with the gaseous mixture of oxygen and inert gas for carrier gas, under normal pressure or vacuum are 0.5 ~ 100mbar condition, carry out Low Temperature Plasma Treating; The input power of plasma treatment is 30 ~ 100W, and plasma treatment time is 5min ~ 100min.
2. a kind of method utilizing plasma gas solid method to activate MoVNbTeOx pure phase M1 catalyst according to claim 1, is characterized in that: low temperature plasma is that a plasma is put in atmospheric dielectric stop.
3. a kind of method utilizing plasma gas solid method to activate MoVNbTeOx pure phase M1 catalyst according to claim 1, it is characterized in that: when carrier gas is the mist of oxygen and inert gas, the ratio of oxygen is 20% ~ 80%.
4. a kind of method utilizing plasma gas solid method to activate MoVNbTeOx pure phase M1 catalyst according to claim 1, is characterized in that: step 1) described in the hydro-thermal method method that obtains MoVNbTeOx mixed phase catalyst comprise the steps:
1) under 60 ~ 80 DEG C of water bath condition, ammonium molybdate, vanadic sulfate and telluric acid are obtained solution A according to the ratio mixed dissolution that the atom of molybdenum and vanadium, tellurium is 1:0.15-0.30:0.15-0.35 in deionized water, ammonium niobium oxalate is dissolved in deionized water and obtains solution B, wherein in niobium and solution A, the atomic ratio of molybdenum is 0.05:1 ~ 0.20:1, the volume ratio of solution A and solution B is 2:1, mix after solution A and solution B are cooled to 30 ~ 50 DEG C and stir, forming precursor solution;
2) precursor solution is placed in water heating kettle, after replacing air wherein with nitrogen, the Hydrothermal Synthesis carrying out 24 ~ 48h at 150 ~ 200 DEG C obtains suspension;
3) suspension obtained by Hydrothermal Synthesis carries out washing and filtering, and grinding after gained sediment spends the night and dries, obtains the solid phase presoma of catalyst;
4) by solid phase presoma 550 ~ 650 DEG C of temperature lower calcinations in nitrogen atmosphere, calcination time is 1 ~ 3h, obtains the mixed phase compound of M1 and M2 in MoVNbTeOx system.
5. a kind of method utilizing plasma gas solid method to activate MoVNbTeOx pure phase M1 catalyst according to claim 1, it is characterized in that: step 1) in obtain pure phase M1 catalyst by MoVNbTeOx system M1 and M2 mixed phase catalyst method be: M1 and M2 mixed phase catalyst is placed in the hydrogen peroxide that volume fraction is 5%, 1 ~ 3h is stirred at 50 ~ 70 DEG C of temperature, then carry out centrifugal, after removing supernatant, dry 12 ~ 24h, namely obtains M1 pure phase catalyst fines in MoVNbTeOx system.
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Cited By (5)
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| WO2018127767A1 (en) * | 2017-01-06 | 2018-07-12 | Nova Chemicals (International) S.A. | Double peroxide treatment of oxidative dehydrogenation catalyst |
| CN108855118A (en) * | 2018-07-17 | 2018-11-23 | 中国科学技术大学 | Preparation method of pure M1 phase MoVTeNBOx catalyst with high specific surface area |
| CN109843434A (en) * | 2016-10-18 | 2019-06-04 | 诺瓦化学品(国际)股份有限公司 | Use the method for hydro-thermal process and peroxide treatment production Oxydehydrogenation catalyst |
| CN114015512A (en) * | 2021-11-23 | 2022-02-08 | 东北农业大学 | Method for applying cold plasma technology activated catalyst to isomerization of safflower seed oil |
| CN115672358A (en) * | 2022-08-17 | 2023-02-03 | 中国科学技术大学 | Preparation method and application of core-shell oxide catalyst for preparing ethylene by oxidative dehydrogenation of ethane |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109843434A (en) * | 2016-10-18 | 2019-06-04 | 诺瓦化学品(国际)股份有限公司 | Use the method for hydro-thermal process and peroxide treatment production Oxydehydrogenation catalyst |
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| CN108855118A (en) * | 2018-07-17 | 2018-11-23 | 中国科学技术大学 | Preparation method of pure M1 phase MoVTeNBOx catalyst with high specific surface area |
| CN114015512A (en) * | 2021-11-23 | 2022-02-08 | 东北农业大学 | Method for applying cold plasma technology activated catalyst to isomerization of safflower seed oil |
| CN115672358A (en) * | 2022-08-17 | 2023-02-03 | 中国科学技术大学 | Preparation method and application of core-shell oxide catalyst for preparing ethylene by oxidative dehydrogenation of ethane |
| CN115672358B (en) * | 2022-08-17 | 2024-04-02 | 中国科学技术大学 | Preparation method and application of core-shell oxide catalyst for preparing ethylene by oxidative dehydrogenation of ethane |
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